CHEM 31.

1 JK-1L

Exercise 2 Purification and Identification Methods of Solid Organic Compounds

Submitted by Rhoda Mae B. Pableo

Group members Maybelle Fortaleza Katia Charmaine Ponce

Submitted to Dominica DM. Dacera, Ph.D.

Abstract There are different purification techniques in purifying organic compounds. Two of these are recrystallization and sublimation. The identity of the purified substance from an unknown compound could also be determined through the use of melting point determination. Unknown A was purified through recrystallization and obtained a purified substance with a percentage yield of 34%. The melting point was determined to be 105C and 106.5C which is quite near to the theoretical melting point of benzoic acid which is 122.35C. Unknown B was purified through sublimation and obtained a purified substance with a percentage yield of 13.20%. The melting point determined ranges from 82.5C and 84.5C. The theoretical and determined melting point was compared and the theoretical melting point was found out to be 80.26C and this substance is naphthalene.

Introduction Several different techniques are used to separate a mixture of organic compounds into its pure components; each has both advantages and limitations. Partitioning a mixture between two solvents--- most commonly water and immiscible solvent such as ethyl ether--- is an effective method for separating compounds that differ in polarity. Recrystallization can be a powerful tool for small- to medium-scale separations if the compound to be purified is crystalline at a convenient temperature. However, because a solvent is involved, such separations can be prohibitive for the very large quantities in the bulk chemistry industry. Distillation is used extensively for large-scale separations, especially in the petroleum industry, where specialized distillation columns can separate compounds, differing in boiling point by only a few degrees. However, only relatively volatile compounds can be purified by distillation (Fox and Whitesen, 1997). In chemistry, recrystallization is a procedure for purifying compounds. The most typical situation is that a desired "compound A" is contaminated by a small amount of "impurity B". Recrystallization of solids is a valuable technique to master because it is one of the methods used most often for purification of solids. Other techniques for purifying solids include sublimation, extraction and chromatography. Nevertheless, even when one of these alternative methods of purification has been used, the solid material thus isolated may still be recrystallized to achieve the highest possible state of purity. The process of recrystallization involves dissolution of the solid in an appropriate solvent at an elevated temperature and the subsequent re-formation of the crystals upon cooling, so that any impurities remain in solution (www.chem.utoronto.ca).

In a process called sublimation, the particles on the surface of a solid absorb enough heat to change directly to a gas with no temperature change and without going through liquid state (Timberlake, 2007). Sublimation is a technique used by chemists to purify compounds. Typically a solid is placed in a sublimation apparatus and heated under vacuum. Under this reduced pressure the solid volatilizes and condenses as a purified compound on a cooled surface (cold finger), leaving a non-volatile residue of impurities behind. Once heating ceases and the vacuum is removed, the purified compound may be collected from the cooling surface (wikipedia.org). On the other hand, another technique can be used in order to be ascertained that your obtained compound from purification is definitely pure. This can be done by determining the melting point and melting point range of the organic compound obtained. When heat is added to a solid, the particles in the rigid structures begin to move faster. At a temperature called the melting point (mp), the particles in the solid gain sufficient energy to overcome the attractive forces that hold them together. The particles in the solid separate and move about in random patterns. The substance is melting, changing from solid state to liquid state (Timberlake, 2007). In order to be able to identify the purity of the obtained substance through determining the melting point and melting point range, finding out the theoretical melting point of the substance can be found out to confirm the identity of our organic compound. Objectives The objectives for this exercise were identified through setting the problem and involving few questions regarding the topic. The main objective of this experiment as stated by the title is to use purification methods to identify solid organic compounds. The specific objectives are as follows: 1. To use different techniques in purification and identification methods 2. To be able to differentiate the techniques in purification and in identification methods
3. To be able to identify solid organic compounds by using these techniques

Methods The materials and procedure of this experiment is adapted from our chemistry lab manual entitled Chemistry 31.1 Organic Chemistry Laboratory. The procedure is found on pages 55-57.

Presentation of Results Table 1 show the details on the first part of the experiment which deals on recrystallization of the first unknown compound which was labeled as unknown A. The impure or given sample is initially weighed and after conducting the experiment on recrystallization, the weight of the crystals obtained is determined. Out of the 1.0 g of crude sample, only 0.34 g of purified crystals making the percentage yield of 34%. The computation of the percentage yield is included in the methodology. Table 1. Weight of samples in the Recrystallization on Unknown A Material Weight (g) 1. Crude Sample 1.0 g 2. Filter paper 0.43 g 3. Filter paper + crystals 0.77 g 4. Purified crystals 0.34 g 5. Percentage yield 34%

The results on sublimation of unknown B are tabulated in Table 2. The weighed crude sample at the beginning of the purification through sublimation is 1.06 g. After purification by sublimation, the obtained purified sample is 0.14 g having a percentage yield of 13.20%. Table 2. Weight of samples in Sublimation on Unknown B Material Weight (g) 1. Crude sample 1.06 g 2. Purified samples 0.14 g 3. Percentage yield 13.20%

Table 3 shows the melting point of unknown A and B determined in the experiment. From where the melting started to the point of complete liquefying of the substance in both samples, the melting point is being recorded. Through this, the melting point is being determined. The determined melting point was obtained through getting the average between the melting point values in the melting point range. The theoretical melting point of both substances was obtained through literature references. The melting point of Benzoic acid is 122.35C (wikipedia. org). The melting point of Naphthalene is 80.26C (wikipedia. org).

Table 3. Melting point determination of Unknown A and B with two (2) trials each. Materials A1 A2 B1 B2 98C 105C 64C 80C Temperature melting starts 112C 108C 105C 85C Temperature melting is complete 98-112C 105-108C 64-105C 80-85C Melting Point Range 105C 106.5C 84.5C 82.5C Determined Melting Point 122.35C 80.26C Theoretical Melting Point Identity of Compound Benzoic acid Naphthalene

Discussion of Results Purification and identification of organic compounds were done by using some techniques such as Recrystallization and Sublimation. Melting point and melting point range determination was used to test and confirm the purity of the substance obtained from the purification techniques. As indicated in Table 1, the obtained purified sample was only 0.34 g out of 1g of crude sample. This means that the impurities from the crude sample is 0.66 g. The percentage yield is 34%. After obtaining this amount after drying the crystals, the melting point of the unknown substance A was obtained and then recorded. Two (2) trials were made to ensure accuracy in the melting point of the substance. The obtained results of melting point are tabulated in Table 2. The substance was known to be benzoic acid due to its properties present and due to the nearness of the determined melting point to its theoretical melting point. On the other hand, the purified samples obtained in substance B weighed 0.14 g from 1.06 g of crude sample. Therefore the impurities which were brought out through sublimation is 0.92 g. The percentage yield of the obtained amount of pure substance is 13.20%. The melting point of the gathered pure substance was determined and the results are tabulated in Table 2. Two (t2) trials were made to obtain the average melting point. The melting point of substance B was determined to be 84.5C and 82.5C. The identity of the substance is Naphthalene since its theoretical melting point according to literature is 80.26C (wikipedia.org).

Conclusion There are different purification techniques in organic compounds. In this experiment, the purification techniques used were recrystallization and sublimation. These techniques were also supported by determination of melting point and melting point range through identification of the compound. There are two substances which are tested. Unknown A was used in recrystallization and Unknown B in sublimation. Both were subjected to determination of melting point and melting point range. Recrystallization and sublimation techniques in purification of an organic compound is effective and accurate since we were able to determine the identity of the two unknown compounds when the melting point was determined by using the purified substance. The identity of the compounds that was determined is Benzoic acid for Unknown A and Naphthalene for unknown B. This was determined through the comparison of the melting points of the unknown compounds to the melting point of benzoic acid and naphthalene.

Question and Answers Pre Laboratory Questions:

1. Referring to the Handbook of Chemistry and Physics, look up the solubility of benzoic acid

in hot and cold water. Indicate why water is a good solvent for the recrystallization of benzoic acid. Benzoic acid is soluble (hot water) 0.34 g/100 mL (and poorly soluble in cold water. Water is a good solvent for the recrystallization of benzoic acid since it is a good solvent of benzoic acid. It can minimize the percentage error and it can also maximize the purity of the substance obtained from the purification of the crude sample.
2. Enumerate three ways you can prevent premature crystallization of solid during hot

filtration. (1) You should use fluted filter paper to maximize the filtering capacity of the filter paper. (2) The crude sample should be completely dissolved in water and after filtration, pour hot water washings to the funnel.(3) The hot water used in filtration should be hot enough and the longer filtration takes place, the better.
3. List possible solvents and mixtures of solvents use to recrystallize sold samples.

Possible solvents for recrystallization of solid samples are water, methanol, ethanol, toluene, and ligroin.

4. How is sublimation different from other purification techniques?

Sublimation is different from other techniques since it lets the impurities from a crude sample to sublime or evaporate first in order for the pure substance to be retained.
5. What is meant by melting point range? What factors may influence this range?

Melting point range is the range of temperature by which melting occurs. From the initial melting when the substance starts to melt up to the complete melting of a substance. The temperature of the bath could affect its range since if it is too hot already, the difference of the initial melting and complete melting would be too little. The amount of the substance could also affect this range since it would take more time to melt invariably greater samples. In general, the melting point range could be affected by purity of the material, size of the tube, and rate of heating bath.
6. To what recommended rate of temperature change should a sample be subjected as the

melting point is approached? Why is the rate important? The temperature of the bath should be uniformly increasing and is slowly heated at the rate of approximately 2C per minute. This is important in order to not affect the melting point range.
7. How much sample should be placed in the capillary tube?

The sample that must be contained in the capillary tube must occupy 1-2mm and s packed tightly inside the tube. Post-Laboratory Questions: 1. How many milliliters of boiling water are required to dissolve 25g acetanilide? If the solution were cooled to room temperature, how many grams acetanilide will remain dissolved when water is cooled at room temperature? How many grams of acetanilide would crystallize out? Solubility of acetanilide in hot water is 5.5 g/100mL at 100C. In cold water, the solubility is 0.53 g/100mL at 0C.

2. What is the effect of the following on the observed melting point of the compound: (a)

insoluble impurity, such as charcoal, (b) incomplete drying of a sample (e.g. the incomplete removal of a recrystallization solvent); (c) less recrystallization solvent was used than it was needed? a. If the charcoal was not dissolved and is included in the determination of the melting point stage, then it would affect the melting point of the substance by increasing of the melting point since impurities are present.
b. The melting point would be lower because of the still wet crystals. It is easier

the melt a sample that it is nearer to liquid state and since the sample is not yet dry, liquid particles are still present. c. Decreasing the recrystallization solvent would not affect the melting point of the substance. Since decreasing the solvent would result to little yield of pure substance due to the fact that little particles were dissolved by the solvent according to its dissolving capacity, the pure substance obtained will also be decreased. This would not affect the melting point because it is an intrinsic property in the sense that the amount would not affect its value.

3. Three test tubes labeled X, Y, and Z, contain substances with approximately the same melting point. How could you prove that the three compounds are different? If X is added to Y or any of the substances is added to another, if the melting point varies, either it increased or decreased greatly, then the substances are different from each other. But if adding any of the substances to another does not greatly affect the melting point, then both or all are same substances. References Book References:

Fox, Marye Anne and James K. Whitesen. 1997.Organic Chemistry 2nd edition. London, UK: Jones and Barret Publishers, Inc. p. 19-3 to 4. Timberlake, Karen C. 2007. General, Organic, and Biological Chemistry Structures of Life 2nd edition. Urong, Singapore: Pearson Education, Inc. publishing as Prentice Hall. p. 234-235. On-line Articles: Naphthalene. Accessed on June 30, 2011. Available from http://en.wikipedia.org/wiki/Naphthalene. Benzoic acid. Accessed on June 30, 2011. Available from http://en.wikipedia.org/wiki/Benzoic_acid Recrystalization. Accessed on June 30, 2011. Available from http://www.chem.utoronto.ca/coursenotes/CHM249/Recrystallization.pdf